Electro Chemistry

Corrosion for Engineers Chapter 13: CORROSION CURRENT
Dr. Derek H. Lister page 13-1
KINETICS OF AQUEOUS CORROSION
Anodic and cathodic reactions are coupled at a corroding metal surface:

MI,el Aqulous environment Metll Aqu.oUI environment
Anodic ,Ite
Anodic sit.
o Oz
cathodic lit"
--'--_R,
Cathodic lit.
---~Rz
(a) (b)
Schematics of two distinct corrosion processes.

(a) The corrosion process M + 0 ~ Mn+ + R showing the separation of anodic
and cathodic sites.
(b) The corrosion process involving two cathodic reactions.
University of New Brunswick, Canada Chulalongkom University, Thailand

Dr. Derek H. Lister page 13 - 2
The "corrosion current" ... ieorr ... related to amount of metal corroded by
Faraday's Law . ..
ieorrt = nFw
M
n =number electrons involved in metal dissolution (~ valency);
F = Faraday constant (96,500 coulomb/mol);
w =mass corroded metal;
M =molecular weight of metal.
Note: there may be more than one cathodic reaction (i.e., more than one "i e")
and more than one anodic reaction (i.e., more than one "ia" ... e.g., for alloy);
ieorr = Li a =. Lie

Also: because areas of anodic regions, As, are generally different from areas of
cathodic regions, A c, CURRENT DENSITIES are generally not equal ... thus ...
while ia = -i c
Aa "* Ac
so la = k."* .k... = Ic ...
Aa Ac
(remember examples of rapid perforation arising from large cathode vs small
anode combinations).
Corrosion consists of charge transfer reactions ... e.g., ...
n
anodic Mlattice ~ M+surface + e ~ M +surface + (n-1)e
cathodic O2surface + 2H+ + e ~ H2 0 2surface

H202 surface + 2H+ + 2e ~ 2H20surface
and mass transport ... e.g., ...
anodic Mn+surface ~ Mn+solution

cathodic 02 solution ~ O2surface
H20surface ~ H20bulk solution

= =
At equilibrium, 'Il 0, E Ee , i 0 but i a =
-i c= =
i o (i.e., the forward and
backward reactions are equal and the rate corresponds to the exchan9.!
current, i o ).
The expression relating the OVERPOTENTIAL, 'Il, to the net current, i, is the
Butler-Volmer equation:
i = i o{exp(P.J1E.'Il) - exp(- [1 - f3].J1E.'Il)}

RT RT
where R = gas constant;
T = absolute temperature;
n = number of charges transferred (valency);
F = Faraday constant (96,500 coulomb/mol);
f3 = "symmetry coefficient" (~ 0.5).
The first term in { } in B-V describes the forward (metal dissolution, anodic)
reaction; the second term in { } describes the backward (metal deposition,
cathodic) reaction.

ACTIVATION CONTROL is when the corrosion is controlled by charge transfer

reactions ...
EITHER the anodic charge transfer OR the cathodic charge transfer can
control.
The anodic reactions and the cathodic reactions in a system can be studied
INDIVIDUALLY by electrochemical methods ... e.g., the changes in potential of
an electrode caused by changes in the current flowing through it (or vice versa)
can be measured ... i.e., we can measure the POLARIZATION.
Consider metal dissolution and metal deposition ...
anodic
M 'M"++ ne
cathodic
If we ."drive" the reaction (with our electrochemical apparatus) in the anodic

direction, we can measure the "overpotential" " (the difference between the
applied potential, E, required to give a net dissolution of metal and the
equilibrium potential, Ee ) and the net current, i.

Dr. Derek H. Lister page 13- 6
A plot of the B-V equation for the metal dissolution/deposition reaction gives
the polarization curve:
Potential
--T--------. M .-... Mn • + ne"

Metal dis.olution
(",), /
E.--l------I-....,· /
r-I
/
i~1.
M'" + ne - . M
Metal deposition (i.l,
••- - Cathodic Current Anodic •

Current-potential relationship for a metal dissolution (M ..... M"Ydepositian (M'· ..... M) protess
If the symmetry coefficient ~ = 0,5, the curve is symmetrical about (i=O, Ee ) •
and the B-V equation has a sinh form.

Note: At large enough overpotentials, the reaction is essentially all in one

direction ... one of the terms in the B-V-E is negligible and can be dropped.
Thus, for metal dissolution:
i a = i o exp(~·n.E·11a)
RT
or 11a = b a log .i (high overpotential or "high-field"
io approximation)
where
ba = 2.303RT ... "Tafel coefficient".
~nF
The Tafel coefficient for metal Q!position:
be = - 2.303RT .
(1 - ~)nF

Note Also: In the narrow region of small overpotentials, the relation becomes
linear ...
In the linear region ...

i = i o .nF.11 (Iow-overpotential or "low-field" approximation).
RT

If a reaction has a large exchange current, i o , the curve is shallow and a large
current is obtained for a small overpotential ...
,
,•
,,
I
.. ,.
I
,
,
I
I
,, ,
,J
, ,
-e.- • , I
,, I
,,
I
(
.... " ,,,

I
•
,
-?(
the reaction is not easily polarized (approaching "non-polarizable").

Dr. Derek H. Lister page 13 -10
If a reaction has a small exchange current, i o , the curve is steep and a large
overpotential is needed for a small current ...
+1\
•••
I
,,
I
. ,I
foi
-c ,,, t-t
,
,
-l'l
the reaction is readily polarized.
Consider now a reaction that is cathodic to the metal dissolution ...

viz.... 0 + ne ~ R
If this is coupled to metal dissolution in the corrosion process, then the
reaction must move away from equilibrium so that a net cathodic current, -ie,
flows ... similarly, the metal dissolution ...
M 4 • Mn+ + ne
must move away from equilibrium so that a net anodic current, -i a, flows.
We know that. .. i a = -i e (= i eorr).
We plot the cathodic reaction on the same diagram as the anodic reaction ... a
La Butler-Volmer ...

Potential
Note: ia = -i c (= icorr) at one

icor, spot on the diagram - the
" pot en t"laI" , Ecorr"
" corrosion
I
/ I
'7
'----.14-,/~
IE) _ _ ..J....,.,
•• /' j' Large (10 ).
Current Anodic _
- Cathodic
Current-potential relationship for a metal dissolution/deposition and an accompanying redox showing

how the two reactions couple together at the corrosion potential, Ecorr •
University of New Brunswick, Canada Chulalongkom Unlverslfy, Thailand

Ecorr is the mixed potential ...

(Ee)a < Ecorr < (Ee)c
Metal dissolution is driven by the ANODIC ACTIVATION OVERPOTENTIAL:
11aA = Ecorr - (Ee)a
and the cathodic reaction is driven by the CATHODIC ACTIVATION
OVERPOTENTIAL:
11cA = (Ee)a - Ecorr
Note: the thermodynamic driving force for corrosion, L\Etherrn ...
L\Etherrn = (Ee)c - (Ee)a.
Usually, L\E therrn is large enough to put Ecorr in the Tafel regions for both
reactions (Le., the reverse reactions are negligible) - unless oxide films
interfere.

The coupled portions of the curves for the anodic and cathodic reactions
(Le., ia + ve, ic + re) are usually plotted as potential vs. logarithm of the current,
with the -ve sign of the cathodic current neglected ...
,
Both curves appear in the +ve
quadrant. This is the "EVANS
DIAGRAM".
Evans diagram for the corrosion process

0+ ne" - R M + 0 ...... M"+ + R
log ;eorr Log (currentl
University of New Brunswick, Canada Chulalongkorn University, Thailand

The straight-line portions of the curves are the TAFEL REGIONS, with Tafel
slopes indicated earlier.
The exchange currents (io)a and (io)c, can be obtained by extrapolating the
Tafel lines back to the equilibrium potentials (Ee)a and (Ee)c ...
N.B. don't forget that the origin (i=O) cannot be shown on a logarithmic plot.
The intersection of the two curves in the Evans diagram occurs at the
corrosion current, icorr.
N.B. the bigger the difference in equilibrium potentials (i.e., the bigger the value
of AEtherm), the bigger the value of i corr (i.e., the greater the corrosion).

Two possible cathodic reactions
NOTE:
•
(E.)~ ~E' therm (= (Ee)c - (Ee)a)
.c-
ftl
< ~E" therm (= (E e" )c - (Ee)a)

1\
-
CI)
f.
E~orr
I so
.' ."
I carr < I corr.
5-
«II
I
E~orr
-F'
II
I 0" + ne- - . R"
I
I
Also: anodic activation
overpotential
, for reaction
•
.
(Ec). I
(E carr - (Ee)a) < for reaction"
0' + ne- -.R' A' A"
(11a ) < (11a ) •
log i~orr log i~orr Log (current)
Evans diagram for a metal dissolution coupled separately to two

cathodic reactions with distinctly different equilibrium potentials,
(Ee}c" and (Ee}c'.
University of New Brunswick, Canada . Chulalongkom University, Thailand

Dr. Derek H. Lister page 13 ·17
Two possible cathodic reactions - different kinetic factors.

Potential
(Ee)~
" ,
Even though (Ee ) c > (Ee ) c,
activation overpotential
, A)', so that
(11/)" < (11a
.
i carr < i corr •• .i.e., the
corrosion couple with the
smaller thermodynamic ,
E~orr driving force (~E therm)
E"c arr produces the larger corrosion
ne· ~ R' current ...
"Kinetics are controlling".
0" + ne- ~ R"
log i~orr log i~orr Log (current)
Evans diagram for a metal dissolution coupled separately to two

cathodic reactions, in which the impact of relative kinetics is
greater than the thermodynamic driving force, AEtherm.

This situation often occurs for a metal corroding in acid, compared with
corroding in dissolved oxygen ... though the thermodynamic driving force is
greater in oxygen (remember, Pourbaix Diagram for Ni), acid corrosion is
faster.
Arises from kinetic factors ...
(l o )w/H1 = 10-3 - 10-2 A1m 2
and (b c)tt/H1 ~ 120 mV/decade (... depending on metal surface)
while ...
(l o )OUHl,o ~ 10-10 A1m 2
and (bc)~lHI,O = 120 mV/decade (... depending on metal surface).

Corrosion Rate Controlled by Anodic or Cathodic Reactions

Overall corrosion rate controlled by SLOWEST reaction ... i.e., reaction with
smallest exchange current, io, and/or largest Tafel coefficient, b.
(Remember, small io means that curve close to vertical axis, large b also means
curve close to axis - with steep slope).
Differences in steepness of curves means that activation overpotentials are
different ... and polarizations are different (steep curve ~ strongly polarized).
Evans diagram showing the Impact on the

corrosion current, Icorro and potential, Ecorr,
of varying the kinetics of a fast metal dissolution
(Alo A z) or a slow cathodic process (C lo Cz).
Cathode reaction in diagram strongly

polarized ... controls corrosion ...
small changes in kinetics of cathode
#0./ ~ Log (current)
have lar9,! effect on corrosion rate,
A log (ico,,)c ~ small changes in kinetics of anode
A log (ico,,). have small effect on corrosion rate.
Mass Transfer Control (not to be confused with EROSION-CORROSION in

which film formation is involved).
If the cathode reagent at the corrosion site (e.g., dissolved 02 in the O2
reduction reaction) is in short supply, mass transfer of the reagent can become
rate limiting.
Then, the cathodic charge-transfer reaction is fast enough to reduce the
concentration of the reagent at the surface corrosion site to a value less than
that in the bulk solution.
ACTIVATION CONTROL MASS TRANSFER CONTROL

From the simple "Nernst Diffusion Layer" model ... flux of cathodic reagent to
surface, J, given by ...
J = • IDCos .Co~
()
so that, at steady state,

lc. = •..Q.{Cos .Co~
nF ()
* In the limit, Cos ~ 0
(i c)lim = nFDC ob = (icorr)max.

()
When corrosion rate is at this limit, it can only be changed by altering the bulk
concentration, Cob, and/or the diffusion layer thickness, (), (by flow, etc.).
University of New Bnmswlck, Canada Chulalongkom University, Thailand

Dr. Derek H. Lister page 13·22
Such "CONCENlRAliON POLARIZAliON" is shown on the Evans diagram

(partial):
-------
Polarization curve for the cathodic process

-
I II
showing activation polarization (point 1), joint
"E
-
Ql
~
........ ....... activation-concentration polarization (point 2),
and transport·limited corrosion control (point 3).
3
Log (current)
Point 1: Small shift from equilibrium potential ... no limitation on reagent

supply· activation control.
Point 2: Control: activation + concentration ... overpotentiailltotal = ll A + ll c
Point 3: Large shift from equilibrium: • reaction rate maximum, ll c infinite.
University of New Brunswick, Canada Chula/ongkom University, Thailand
Dr. Derek H. Lister page 13· 23
Effect of increasing mass transport rate (e.g., by stirring the solution

surrounding a corroding surface) ...
(~c - - - - - - - - - - - - - - - - - -
...
.!!
cQ)
...
&. Evans diagram for a corrosion process
initially controlled by the transport of
cathodic reagent to the corroding surface
-- (line 1). lines 2 and 3 show the effect of

increasing the transport rate of reagent.
1 2
2 log (current)
•
log i corr
Increase in corrosion potential, Ecom caused by decrease in cathodic

overpotential as concentration polarization decreased.
If anodic reaction were mass-transfer controlled (difficulty of metal
ions diffusing away), improved stirring would DECREASE Ecorr • I DISCUSS I
Electrochemical methods for studying corrosion (e.g., evaluating the

performance of a metal specimen in a test solution) often involve the
construction of POTENTIAL vs CURRENT curves ... i.e., they involve the study
of polarization characteristics.
Polarization Measurements
The simple potentiostat for applying a fixed potential (relative to a reference
electrode) and measuring the current (flowing from the "working" electrode to
the "counter" or "auxiliary" electrode):
4' Very low

res istC1nceL:::~=d A typical arrangement of a classical potentiostat.
mY
Meter
counter.
electrod~e~~
Probe * ensures specimen potential (w.r.t.
counter) constant ... even though
solution resistance might alter.
University of New Brunswick, Canada Chulalongkorn University, Thailand
REMEMBER: We can only measure the net current across the specimen
electrode - at the corrosion potential there is no net current (only local anode-
cathode currents which constitute the corrosion current). WE CANNOT
MEASURE CORROSION RATE DIRECTLY ...although i corr is what we need!
Tafel Method
Measure potential and current at some distance on either side of Ecorr and
extrapolate E - log i curves (in same quadrant) back to Ecorr •••
.......-5lope = b~'
Plot of the total current (ir = io + ie ) versus
o + ne- -.- R potential showing the extrapolation of the
Tafel regions to the corrosion potential,
Eeom to yield the corrosion current, ieorr •
Log (current)
log (icorr)

N.B. If we know ... (for the anodic or cathodic reaction)

- the exchange current, (io)a, say;
- the equilibrium potential, (Ee)a;
- the Tafel coefficient, b a,
then from one measurement (of the corrosion potential, Ecorr) we can
calculate the corrosion rate ...
icorr = io exp{2.303~
ba
We don't usually, know these, though.

Linear Polarization Method

Valid for corrosion under activation control.
Involves applying small perturbations to the potential around Eeorr (i.e., ~E ~ 10 mV).
-. ..... '.
.
.
~."~Iil(
~) Over small AE (~20mV) the
curves are approximately linear
" with slopes:
Sa = gs = b!!,
di 2.303 i eorr
and ISe I = dE = be
di 2.303 i eorr
AI:. --- and from the linear geometry ...
~ -- --,- ''''', Ai = ...s.a~el
I
I AE s:TSJ
tM'/s..l !
. which gives ...
---_.--
-(.
ieorr = 1 .~ Ai
2..303 ba+ Ibe I AE
The "polarization resistance", Ai/AE, is measured: the Tafel coefficients ba and be must
be known.

Passivation
Under certain conditions of potential and pH, some metals form protective
f I·1 ms ... I.e.,
. th ey " passlva
. t"e :
"'i
.~
Q) Pourbaix diagram for the
(5
Q. ironlwater/dlssolved oxygen system
showing the effect of potential In moving
the system from a corrosive (active) region
(point 1) to a passive region (point 2).
pH
We can examine the KINETICS via an Evans diagram ...

The polarization curve for the ANODIC reaction of a passivating metal drawn
for potentials more noble than the equilibrium potential (Ee)a ...
Oxygen evolution
H20 ...... O2
------------
Transpassive
Oxidative dissolution of oxide
M ° .... MIn .. 11.... (e.g., Cr203 CrOll
Jl Y
(E.)M/MO Is the equilibrium potential for

oxide/hydroxide formation.
Tafel region (l cr1t Is minimum reaction

---------- rate required to Initiate film growth by
precipitation of Mn+).
Log ip .... log ieril

Log (currentl
The region attained by the metal in a given environment depends upon the
cathodic reaction ... i.e., where the cathodic curve "cuts" the above anodic
curve.
Cathodic Reaction 1: (E e )c1 < Epass,

so (Ecorr)1 must also < Epass ...
corrodes actively.
Cathodic Reaction 2: (E e )c2 > Epass ;
HOWEVER, curve intersects Tafel line
Epe.. - for anodic reaction BELOW icrit ...
(E.l el
passive film cannot form, corrodes
(Eeor~ ~:.;;~c::::
(Eeorr ), (E.). LL":':"'-..I--~~~--- actively.
1 2 log jerol
3 Cathodic Reaction 3: both passivating
. I
log ieorr condition are met ((E e )c3 > Epass ;

Log (current) iinitial (intersecting Tafel line) > i crit) ...
passivates.
Impact of various cathodic reactions on the
corrosion current and potential for a metal
capable of undergoing an active-passive transition.

Other Corrosion Examples on Evans Diagrams (from Fontana)
Velocity Effects
c
'OOlid
0+- E'Ol.id
t
i€
C tncrem;ing _
iOM
t €M
. " ' - ",' A
\ 2 :3 4 5
velocity
D
3 4 5
log ,.
Effect of velocity on the electrochemical Effect of velocity on the corrosion rate

behaviour of an active-passive metal of an active-passive metal corroding under
corroding under diffusion control. diffusion control.

Galvanic Effects
Isolated zinc corrodes in acid ...
Zn ~ Zn 2+ + 2e
2H+ + 2e ~ H2
Platinum is inert in acid, BUT, when coupled ... zinc corrosion increases,
H2 evolution occurs on platinum ...
NOTE:
+ the thermodynamic
driving force remains the
1
£
£couPle I
I
same
=
(~Etherrn (Ee)H"1Hz - (Ee)ZnlZnh )
I but the kinetics change -
~
£1;0" I EXCHANGE CURRENTS on
I
Zn and Pt are different:
il;o,rlZnl
+
'I;orrl~-Ptl
Potential increases,
,'£ +z
Zn/Zn
'HzIZnl 'HzIZn-e!1 H2 evolution on Zn
decreases, total reaction
log i increases.
Effect of galvanically coupling zinc to platinum (equal areas).

Effect of H+/Hz Exchange Current

The more efficient the hydrogen evolution process (i.e., the higher the
exchange current), the larger the effect of galvanic coupling ...
Totol reduction rote (ind. nd~c,t,~ If\~)
i
E
EH'/H,
~ 'Z.e
'corr!Z~ -Ptl
fezn ",1.
1
- EZn/ZnH L
tI 1.(\'"'"1.f'
'corr! Znl
_
log "
Comparison of zinc-platinum and zinc-gold galvanic couples (equal areas).

. ....
Pt is a very efficient cathode.
University of New Brunswick, Canada Chuiaiongkom University, Thailand

Effect of Cathode Surface Area
Totol reduction rote
.-t
'0H lPt,10 emI! )
z
+
Effect of cathode-anode
area ratio on galvanic
E corrosion of zinc-platinum
couples.
! ,~
log current
Increasing cathode area increases corrosion; (remember, corrosion [mixed]

potential determined by point where total oxidation rate equals total reduction
rate ... rates of individual processes determined by mixed potential).
I"" " I
.
corr 1M)
"
+ "
",. '''---Toto I oxidation
£
t£""" rate
1 i corr (N) Galvanic couple between

two corroding metals.
log ,.
• more active metal corrodes faster when coupled, more noble metal
corrodes slower;
• more active metal becomes anode, more noble becomes cathode;
N.B. actual rates depend on Tafel slopes, exchange currents, etc., ...
without detailed information we only predict trends.
UnIversity of New BrunswIck, Canada Chulalongkom UnIversity, Thailand
Effects on Passivating Metals
Spontaneous passivation of titanium

by galvanically coupling to platinum.
::::"~--ECOrr(Til
log;
Only works if passivating potential (i.e., Flade potential) less than EHz!H~.
NOTE: Raises the possibility of ANODIC PROTECTION.

I
I
Galvanic couple between an

active-passive metal and
E
t platinum in air-free acid
solution.
! 'corr(M 1
'corr( ~-Ptl
log ,.
Passivating potential too noble for couple to passivate metal.

If very large Pt cathode coupled, corrosion can be increased to P.

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Corrosion for Engineers Chapter 13: CORROSION CURRENT

Dr. Derek H. Lister page 13-1

KINETICS OF AQUEOUS CORROSION

Anodic and cathodic reactions are coupled at a corroding metal surface:

Schematics of two distinct corrosion processes.

University of New Brunswick, Canada Chulalongkom University, Thailand

University of New Brunswick, Canada Chulalongkom University, Thailand

cathodic O2surface + 2H+ + e ~ H2 0 2surface

anodic Mn+surface ~ Mn+solution

University of New Brunswick, Canada Chulalongkom University, Thailand

i = i o{exp(P.J1E.'Il) - exp(- [1 - f3].J1E.'Il)}

University of New Brunswick, Canada Chulalongkom University, Thailand

ACTIVATION CONTROL is when the corrosion is controlled by charge transfer

If we ."drive" the reaction (with our electrochemical apparatus) in the anodic

University of New Brunswick, Canada Chulalongkom University, Thailand

--T--------. M .-... Mn • + ne"

••- - Cathodic Current Anodic •

If the symmetry coefficient ~ = 0,5, the curve is symmetrical about (i=O, Ee ) •

and the B-V equation has a sinh form.

University of New Brunswick, Canada Chulalongkom University, Thailand

Note: At large enough overpotentials, the reaction is essentially all in one

University of New Brunswick, Canada Chulalongkom University, Thailand

In the linear region ...

University of New Brunswick, Canada Chulalongkom University, Thailand

.... " ,,,

University of New Brunswick, Canada Chulalongkom University, Thailand

Consider now a reaction that is cathodic to the metal dissolution ...

University of New Brunswick, Canada Chulalongkom University, Thailand

Note: ia = -i c (= icorr) at one

Current-potential relationship for a metal dissolution/deposition and an accompanying redox showing

University of New Brunswick, Canada Chulalongkom Unlverslfy, Thailand

Ecorr is the mixed potential ...

University of New Brunswick, Canada Chulalongkom University, Thailand

Evans diagram for the corrosion process

log ;eorr Log (currentl

University of New Brunswick, Canada Chulalongkorn University, Thailand

University of New Brunswick, Canada Chulalongkom University, Thailand

Two possible cathodic reactions

< ~E" therm (= (E e" )c - (Ee)a)

Evans diagram for a metal dissolution coupled separately to two

University of New Brunswick, Canada . Chulalongkom University, Thailand

Two possible cathodic reactions - different kinetic factors.

log i~orr log i~orr Log (current)

Evans diagram for a metal dissolution coupled separately to two

University of New Brunswick, Canada Chulalongkom University, Thailand

University of New Brunswick, Canada Chulalongkom University, Thailand

Corrosion Rate Controlled by Anodic or Cathodic Reactions

Evans diagram showing the Impact on the

Cathode reaction in diagram strongly

Mass Transfer Control (not to be confused with EROSION-CORROSION in

ACTIVATION CONTROL MASS TRANSFER CONTROL

University of New Brunswick, Canada Chulalongkom University, Thailand

so that, at steady state,

(i c)lim = nFDC ob = (icorr)max.

University of New Bnmswlck, Canada Chulalongkom University, Thailand

Such "CONCENlRAliON POLARIZAliON" is shown on the Evans diagram

Polarization curve for the cathodic process

Point 1: Small shift from equilibrium potential ... no limitation on reagent

Effect of increasing mass transport rate (e.g., by stirring the solution

-- (line 1). lines 2 and 3 show the effect of

Increase in corrosion potential, Ecom caused by decrease in cathodic

Electrochemical methods for studying corrosion (e.g., evaluating the

4' Very low

University of New Brunswick, Canada Chulalongkom University, Thailand